JPH02147621A - Epoxy resin having imide ring, preparation thereof and epoxy resin composition containing the same resin - Google Patents

Abstract

PURPOSE:To improve adhesiveness, heat resistance and mechanical characteristic by reacting an imide ring-contg. diphenol with an epichlorohydrin. CONSTITUTION:A tetracarboxylic acid dianhydride (a) of formula I (wherein R is a 2C or higher aliph. group alicyclic group, monocyclic aliph. group, condensed polycyclic arom. group or non-condensed polycyclic arom. group wherein arom. groups are connected to each other directly or through a crosslinking bond) is reacted with 2-(3-hydroxyphenyl)-2-(4-aminophenyl)propane or 2-(4- hydroxyphenyl)-2-(4-aminophenyl)propane (b) in a polar solvent which does not participate in the reaction to obtain one of amic acid-contg. diphenols of formula II (wherein both OH groups are bound to the m- or p-positions), which is they dehydrated by heating to obtain one of imide ring-contg. diphenols (A) of formula III. The component A is reacted with an epihalohydrin (B) (e.g. epichlorohydrin) in the presence (absence) of a hydrogen halide acceptor at 40-120 deg.C to obtain the title resin wherein 50% or more of OH groups of the component A are epoxidized.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel and useful epoxy resin composition that has liquid properties, heat resistance, and mechanical properties. The present invention also relates to a novel epoxy resin obtained by reacting a diphenol having an imide ring with shrimp halohydrin as the epoxy resin component, and a method for producing the same.

[Conventional technology]

Epoxy resins have excellent mechanical and electrical properties and adhesive properties, and have been used in a wide variety of fields as high-performance resins such as adhesives, paints, and sealants. Epoxy resins that can be used for these purposes include 2.2-bis(4-hydroxyphenyl)propane, phenol novolac resin, orthocresol novolak resin, 4.4'-methylene dianiline, 4,4'- The typical basic type is a polyfunctional epoxy resin derived from diaminodiphenylsulfone and shrimp halohydrin, and has met various performance requirements in various fields. Furthermore, these epoxy resins are combined with known curing agents or, if necessary, curing accelerators, fillers, etc., and used in various applications.

However, in recent years, the field of application of epoxy resins has expanded to cutting-edge fields such as high-performance composite materials and electronic materials for the space and aircraft industries, and the performance requirements for matrix resins and adhesives in these cutting-edge fields are extremely high. It is difficult for conventional epoxy resins to satisfy various performance requirements.

In particular, there are almost no known epoxy resin compositions that can simultaneously satisfy the required properties such as heat resistance, adhesiveness, and mechanical strength.

[Problem to be solved by the invention]

The present invention has been made to overcome the problems and drawbacks of the prior art described above.

An object of the present invention is to provide an epoxy resin with well-balanced performance that has high standards of performance required in the field of advanced technology, ie, heat resistance, adhesiveness, mechanical strength, etc.

Another object is to provide a method for producing a resin such as (.

A further object is to provide an epoxy resin composition containing such an epoxy resin as a main component.

[Means to solve the problem]

The present invention capable of achieving the above object has the following configuration.

That is, the present invention provides - formula (I) (wherein R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group, an aromatic group) directly,
or a non-fused polycyclic aromatic group interconnected by a bridge member, and the two hydroxy groups are both bonded to the meta or para position) and imide ring-containing diphenols and shrimp halohydrin. An imide ring-containing epoxy resin obtained by reaction and a method for producing the same,
This is a resin composition in which the epoxy resin is an essential epoxy component, and the epoxy resin component is blended with a curing agent and, if necessary, a curing accelerator.

The cured product obtained from the resin composition of the present invention shows a dramatic improvement in heat resistance due to the use of an epoxy resin containing an imide ring that does not participate in the curing reaction. Also, 2
, 2'-bis(hydroxyphenyl)propane type skeleton, and because it is cured by the epoxy group connected to it, it exhibits excellent mechanical strength and adhesive properties.

The method for producing the epoxy resin of the present invention will be described. First, a theoretical amount or a small excess amount of 2-(3-hydroxyphenyl ) -2-(4
-aminophenyl)propane or 2-(4-hydroxyphenyl)-2-(4-aminophenyl)propane is reacted in a polar solvent that does not participate in the reaction, and the following general formula (b) (wherein R is the general formula (Same meaning as (I), both hydroxy groups are bonded to meta or para position)
Producing amic acid-containing diphenols represented by
Furthermore, this amic acid-containing diphenol is heated to an appropriate temperature and subjected to a dehydration reaction to produce an imide ring-containing diphenol represented by formula (I).

Examples of the tetracarboxylic dianhydride used include ethylenetetracarboxylic dianhydride, 1, 2.3.
4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride,
3.3°, 4.4'-benzophenonetetracarboxylic dianhydride, 2.2°, 3.3°-benzophenonetetracarboxylic dianhydride, 3.3°, 4.4°-biphenyltetracarboxylic acid dianhydride, 2,2", 3°3°-biphenyltetracarboxylic dianhydride, 2,2-bis(3,
4-dicarboxyphenyl)propanihydride, 2.2
-bis(2,3-dicarboxyphenyl)propanihydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfonic anhydride, 1.1-bis(2 ,3-dicarboxyphenyl)ethane dianhydride, bis(2゜3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2.3.6.7-naphthalenetetracarvone Acid dianhydride, 1,4.5.8-naphthalenetetracarboxylic dianhydride, 1,2.5.6-naphthalenetetracarboxylic dianhydride, 1.2,3.4-
Benzene tetracarboxylic dianhydride, 3, 4.9.10
-perylenetetracarboxylic dianhydride, 2.3,6.7
-Anthracenetracarboxylic dianhydride, 1,2,7
．． 8-anthracentetracarboxylic dianhydride, 1.2
．． 7.8-phenanthrenetetracarboxylic dianhydride,
Examples include 1,3-bis(3,4-dicarboxyphenoxy)phenyl dianhydride.

As a reaction solvent, N,N-dimethylacetamide, N
, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,
N-diethylacetamide, phenol, cresol,
Organic polar solvents that do not participate in the reaction, such as hexamethylphosphoramide, tetramethylurea, dimethylsulfoxide, dimethylsulfone, sulfolane, and dimethylsulfolane, are used alone or in combination with other solvents, and furthermore, benzene, toluene, xylene, It can be used in combination with a solvent such as cyclohexane.

The reaction temperature is about 50°C or less, preferably about 40°C or less, more preferably about 20 to about 25°C during the first step of producing the amic acid-containing diphenol; The reaction is allowed to proceed until the production of phenols is sufficiently completed. Reaction times are typically 0.5 to about 15 hours.

Furthermore, the reaction temperature in the second stage reaction, in which the amic acid-containing diphenols obtained by the above reaction is thermally dehydrated and cyclized to produce imide ring-containing diphenols, is usually about 100℃.
The reaction temperature is about 300° C., preferably about 130° C. to about 250° C., and the reaction is carried out at the same temperature for a sufficient time until the production of the imide ring-containing diphenols is completed. Usually about 1 to about 15 hours is sufficient.

The imide ring-containing diphenols produced by the above operation can be obtained as crystals by cooling the reaction solution or discharging it into a solvent such as water or methanol.

The imide ring-containing diphenols thus obtained can be epoxidized using a known method.

That is, imide ring-containing diphenols and shrimp helohydrin, preferably epichlorohydrin, are heated at a temperature of about 40 to about 120°C, preferably about 80 to about 120°C, in the presence or absence of a hydrogen halide acceptor. By reacting within this range, the desired imide ring-containing epoxy resin can be obtained. In addition, the shrimp herohydrin used in the 0 reaction, in which an epoxide can be obtained by simply heating a mixture of imide ring-containing diphenols and shrimp herohydrin within the above temperature range, has a molar equivalent to active hydrogen. amount or more, preferably about 3 to about 100 times the mole, more preferably about 10 to about 50 times the mole.

In addition, from the point of view of uniformity and smoothness of the reaction, it is also possible to carry out the reaction using an organic solvent if necessary. In this case, the solvents used include sulfolane, dimethylsulfolane, and N-methyl-2. -pyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoramide and the like.

Although the amount of solvent is not particularly limited, it is usually O to SO(
It is used in an amount of 0 to 20 times (by weight), preferably 0 to 20 times (by weight), and the amount is preferably such that the reaction solution becomes a completely homogeneous solution.

Further, hydrogen halide acceptors used in the present invention include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide, sodium formate, and sodium acetate. Organic acid alkali salts, organic amines such as trimethylamine and triethylamine, alcoholades such as sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide are used, and among them, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are used. Preferably.

These are added as an aqueous solution or a solid, and the concentration of the aqueous solution may be arbitrary, but from the viewpoint of efficiency, it is desirable to have a concentration of 40% or more.

By gradually adding a hydrogen halide acceptor to the mixture of imide ring-containing diphenols and shrimp halohydrin at the above reaction temperature, glycidyl ether is produced via herrohydrin ether produced by addition of shrimp halohydrin. During the reaction, filtrate water is produced as a by-product and exists in the system, so if shrimp halohydrin and water distill out azeotropically, they will be separated using a water separator, the water will be removed from the system, and shrimp halohydrin will be distilled off. is returned to the system to keep the concentration of the reaction solution constant.

After the reaction, if the target product is obtained in solid form, the epoxy resin can be obtained by filtration, but if it is obtained in solution form, the excess shrimp halohydrin or organic solvent must be distilled off, or the precipitation solvent A solid imide ring-containing epoxy resin can be obtained by using these methods or by a combination of these methods.

Methanol, ethanol, isopropanol, acetone, benzene, toluene, xylene, hexane, etc. can be used as the precipitation solvent.

In addition, by-produced inorganic salts can be removed by means such as filtration or washing with water.

In the epoxy resin obtained by the above method, it is desirable that 50% or more of the hydroxyl groups of the imide ring-containing diphenol are epoxidized.

Next, the epoxy resin composition of the present invention will be explained.

The resin composition of the present invention is a resin composition in which the epoxy resin obtained by the above method is an essential epoxy component, and the epoxy resin component is blended with a curing agent and, if necessary, a curing accelerator. be.

In the present invention, it goes without saying that other types of epoxy resins may be used in combination, and typical examples of such types of resins include monohydric phenols such as phenol and aralkylphenol. Novolak resins ZJi obtained by condensation of formaldehydes and formaldehydes: 2.2-bis(4-hydroxyphenyl)propane (common name: bisphenol A), bis(4-hydroxyphenyl)methane (common name: bisphenol F)
or polyfunctional epoxy resin obtained by reacting shrimp halohydrin with a hydroxyl component such as bisphenols such as bis(4-hydroxyphenyl)sulfone (common name: bisphenol S); metaphenylenediamine, diaminotoluene, 4゜4 A polyfunctional epoxy resin obtained by reacting shrimp halohydrin with an amine component such as °-methylene dianiline, 3.3゛-diaminodiphenylsulfone, 4,4゛-diaminodiphenylsulfone;
Epoxy resins derived from aminophenols, phthalic acids, hydantoins, etc.: Other known and commonly used epoxies (including M resin).

When the epoxy resin of the present invention and the above-mentioned known and commonly used epoxy resin are used together, in order for the composition of the present invention to exhibit excellent performance in terms of adhesion, heat resistance, and mechanical strength, the ratio of the former to the latter must be adjusted to a known level. Including the case where a conventional epoxy resin is not used together, the ratio of the former needs to be within the range of 100/O to 20/80 (weight ratio), preferably 30% by weight or more.

In particular, as an epoxy component, the epoxy resin of the present invention is used in an amount of 15% by weight or more in the total epoxy resin composition, and if necessary, other known and commonly used epoxy resins are also used in combination with the present invention. This constitutes the epoxy resin composition of the invention.

In the present invention, as the curing agent constituting the composition, all compounds commonly used as curing agents for epoxy resins can be used, but representative ones include H, Lee, etc. Other authors, “Handbo
ok of the Epoxy Re5in- and other publications, and particularly preferred are novolac resins,
Examples include alicyclic amines, aromatic amines, aromatic amine-formaldehyde condensates, guanidine derivatives, dicyandiamide, and polybasic acid anhydrides.

In many cases, in order to use each of the compounds listed above as a curing agent, it is necessary to also use a curing accelerator, but in such cases, tertiary amines such as dimethylbenzylamine, imidazoles, etc. All known and commonly used curing accelerators can be used, including the compounds described in the publications listed above, such as various metal compounds.

The composition of the present invention may further contain various known and commonly used additives such as fillers, colorants, flame retardants, mold release agents, and coupling agents, if necessary.

The curable resin composition of the present invention obtained in this way is
It exhibits excellent performance in adhesiveness, heat resistance, and mechanical strength, and is extremely useful as a matrix resin for composite materials and adhesives in addition to molded and cast products.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.

Synthesis Example 1 1.2-(4-hydroxyphenyl)-2-(4° -aminophenyl)propane 47,7
g (0,21 mol) and 33.8 g (0
, 105 mol).

Next, stirring was carried out at room temperature for 15 hours, and then the reaction solution was heated and stirred at 150 to 170°C for about 5 hours.

After the reaction is complete, cool to room temperature and add 250 mn of methanol.
When the mixture was charged and stirred, pale yellow imide ring-containing diphenol was precipitated. The pale yellow crystals were filtered and N
, N-dimethylacetamide and methanol mixture, washed with 50N+J2 methanol, and dried to obtain 63.7 g of pale yellow powder.

Purity by high performance liquid chromatography was 99.0%.

Other analysis results are shown below.

Melting point 250-256℃ Elemental analysis value C4tHsaN20yCHN Calculated value (%) 76.22 4.86 3.78 Analysis value (%) 75.83 4.53 3.76M5 C
FD method) Near 41' ◆1) IR (Ni B 'tablet method): 1600 cm-' (carbonyl group) 1720, 1770 cm-' (carbonyl group of imide ring) 3480 cm-' (hydroxyl group) Obtained by the above Imide ring-containing diphenol 51, 8
g (0.07 mol) using a stirrer, thermometer,
A reaction vessel equipped with a Stark water separator and a reflux condenser was charged with 350 g (3.8 mol) of epichlorohydrin.
) and continued stirring at 110-115°C until complete dissolution.

Then, 40% while maintaining a temperature of 110-115℃
16.8 g of aqueous sodium hydroxide solution was added dropwise over 3 hours. Of the water and epichlorohydrin that azeotroped, water was discharged from the system and epichlorohydrin was returned to the system.

After the dropwise addition was completed, stirring was continued for another 15 hours while maintaining the same temperature. After the reaction was completed, the inorganic salts were removed by suction filtration at room temperature, and the reaction solution was further concentrated until the total m was about 120+nI2. This concentrated solution was dropped over 2 hours into 1500 mρ of isopropyl alcohol that was being stirred vigorously to precipitate a yellow powdery imide ring-containing epoxy resin.

This yellow powder was filtered, washed with 200 mβ isopropyl alcohol, and dried to obtain 56.3 g of the desired imide ring-containing epoxy resin in the form of a yellow powder.

The epoxy equivalent of this epoxy resin is 482.5g/eq
The softening point was 118-128°C.

The results of IR analysis are shown in Figure 1.

Synthesis Example 2 250 ml of N,N-dimethylacetamide subjected to water removal treatment in a reaction vessel equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube 1.2-(4-hydroxyphenyl)-2-(4° -aminophenyl)propane 47.7
g (0.21 mol) and pyromellitic dianhydride 2
2.9 g (0,105 mol) is charged.

Next, stirring was carried out at room temperature for 15 hours, and then the reaction solution was heated and stirred at 150 to 170°C for about 5 hours.

After the reaction was completed, yellow crystals of imide ring-containing diphenol were precipitated by cooling. The yellow crystals were filtered out and 2
0n+12 N,N-dimethylacetamide and 50m!
After washing twice with methanol in step 2 and drying, the result was 61.0.
g of yellow powder was obtained.

The analysis results are shown below.

Melting point 300℃ or higher Elemental analysis value C4゜■3□Nz0sCHN Calculated value (%) 75.50 5.03 4.40 Analysis value (
%) 75.20 4.86 4.49M5 (FD
method), 535 +M'111R (Br tablet method)
: 1700,1765 am-' (carbonyl group of imide ring) 3400 cm-' (hydroxyl group) Imide ring-containing diphenol 44, 5 obtained above
g (0.07 mol) using a stirrer, thermometer,
/・;l.

A reaction vessel equipped with a turf water separator and a reflux condenser was charged with 64.8 g of epichlorohydrin (0.7 mo
l), mixed with sulfolane 400n+j2, 110~
Stirring was continued until complete dissolution at 115°C.

Next, 16.8 g of a 40% aqueous sodium hydroxide solution was added dropwise over 3 hours while maintaining the temperature at 110 to 115°C.

After the dropwise addition was completed, stirring was continued for another 30 hours while maintaining the same temperature. After the reaction is complete, cool to room temperature and add methanol 20
Discharge into 0nl, filter off the yellow powder, and further heat at 80m℃.
Washing was performed with methanol.

This yellow powder was vigorously stirred in 200 mβ of water,
After removing the inorganic salts, add 100mβ water twice for 10 minutes.
After washing once with 0 mI2 methanol, drying yields the desired yellow powdery imide ring-containing epoxy resin 51.3
I got g.

The epoxy equivalent of this epoxy resin was 4415 g/eq, and the softening point was 162 to 171T.

Synthesis Example 3 In the reaction of Synthesis Example 1, instead of 3.3°, 4.4″-benzophenonetetracarboxylic dianhydride, 3.3°, 4,4
°-Diphenyl ether tetracarboxylic dianhydride 32
．． Using 6 g (0.105 mol), 52.8 g of the corresponding imide ring-containing epoxy resin was obtained.

Epoxy equivalent is 475g/eq, softening point is 98-10
The temperature was 5°C.

Synthesis Example 4 250 ml of N,N-dimethylacetamide subjected to water removal treatment in a reaction vessel equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube 1.2-(3-hydroxyphenyl)-2-(4° -aminophenyl)propane 47,
7 g (0.21 mol) and 33.8 g (
105 mol).

Next, stirring was carried out at room temperature for 5 hours, and then the reaction solution was heated and stirred at 150 to 170°C for about 15 hours.

After the reaction is complete, cool to room temperature and add methanol to 250 mβ.
When the mixture was charged and stirred, pale yellow imide ring-containing diphenol was precipitated. The pale yellow crystals were filtered and N
, N-dimethylacetamide and methanol mixture, washed with 50 ml of methanol, and dried to obtain 64.7 g of pale yellow powder.

Purity by high performance liquid chromatography was 99.7%.

Other analysis results are shown below.

Melting point 188-191°C Elemental analysis value C4JsllNzOtC)IN Calculation (1ii (%) 76.22 4.86 3.
78 analysis value (%) 75.92 5.00 3.97
M5 (FD method), 7411M4+11 R (KB
r tablet method): 1660 cm-' (carbonyl group)
1720.1770 cm-' (carbonyl group of imide ring) 3480 cm-' (hydroxyl group) Imide ring-containing diphenol 51, 8 obtained above
g (0.07 mol) was charged into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, mixed with 485 g (5.25 mol) of epichlorohydrin, and 95 to 10
After stirring for 5 hours in a completely dissolved state at 5°C, the reaction was completed.

The resulting reaction solution was cooled to 70°C, and 460 g of excess epichlorohydrin was recovered at 70°C or lower by vacuum distillation. Add 150 parts of isopropyl alcohol to this concentrate.
When the mixture was stirred at 60° C. or below for 15 minutes, it was separated into an oil layer and an alcohol layer. When this oil layer was discharged into 225 g of isopropyl alcohol which was being vigorously stirred, 55.7 g of a yellow powdery imide ring-containing epoxy resin was obtained.

The epoxy current of this epoxy resin is 479.5g/eq
The softening point was 95 to 105°C.

The IR analysis results are shown in Figure 2.

Synthesis Example 5 250 ml of N,N-dimethylacetamide subjected to water removal treatment in a reaction vessel equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube aminophenyl)propane 47,7
g (0.21 mol) and pyromellitic dianhydride 2
2.9 g (0,105 mol) is charged.

Next, stirring was carried out at room temperature for 15 hours, and then the reaction solution was heated and stirred at 150 to 170°C for about 5 hours.

After the reaction was completed, it was cooled and discharged into 900 m of water to precipitate yellow crystals of imide ring-containing diphenol. The yellow crystals were filtered, washed twice with 2Qnl of N,N-dimethylacetamide and 5Qnl of methanol, and dried to obtain 61.2g of yellow powder. Purity by high performance liquid chromatography was 99.2%.

The analysis results are shown below.

Melting point 300℃ or higher Elemental analysis value C4゜Hs2N20gC)IN Calculated value (%) 75.50 5.03 4.40 Analysis value (%) ? 5.10 4.79 4.20M5 (
FD method): 636"" IR (or tablet method): 17004765 cm
-' (carbonyl group of imide ring) 3400 cm-+ (hydroxyl group) Imide ring-containing diphenol 44, 5 obtained above
g (0.07 mol) was placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, and mixed with 485 g (5.25 mol) of epichlorohydrin.
The reaction was completed by stirring for 5 hours while the solution was completely dissolved at ℃.

The resulting reaction solution was cooled to 70°C, and 300 g of excess epichlorohydrin was recovered at 70°C or lower by vacuum distillation. When this concentrated liquid was discharged into 300 mfi of vigorously stirred methanol, a yellow powdery imide ring-containing epoxy resin was precipitated. This epoxy resin was filtered, washed with 10 mI2 of mechnol, and dried to obtain 51.5 g of imide ring-containing epoxy resin. The epoxy equivalent of this epoxy resin is 443.5g/
eq, and the softening point was 156-166°C.

The results of IR analysis are shown in Figure 3.

Synthesis Example 6 250 ml of N,N-dimethylacetamide subjected to water removal treatment in a reaction vessel equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube 1.2-(3-hydroxyphenyl)-2-(4') -aminophenyl)propane 47,7
g (0,21 mol) and 32.6 g (0,105
mol).

Next, stirring was carried out at room temperature for 5 hours, and then the reaction solution was heated and stirred at 150 to 170°C for about 15 hours.

After the reaction is complete, cool to room temperature and add 250 mI of methanol.
When the mixture was charged and stirred, pale yellow imide ring-containing diphenol was precipitated. The pale yellow crystals were filtered and N
, N-dimethylacetamide and methanol mixture, washed with 50 mβ methanol, and dried to obtain 64.7 g of pale yellow powder. Purity by high performance liquid chromatography was 99.2%.

The analysis results are shown below.

Melting point 166-168℃ or higher Elemental analysis value C411H36N207CHN Calculated value (%) ? 5.80 4.95 3.85 Analysis value (%) 75.6Q 4.51 3.76M5
(FD method), 729+1'+1) IR (KBr tablet method): 1240 cm-' (ether group) 172
0,1770 am-' (carbonyl group of imide ring) 3400cn+-' (hydroxyl group) Imide ring-containing diphenol 51,8 obtained above
g (0.07 mol) was placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, and mixed with 485 g (5.25 mol) of epichlorohydrin.
After stirring for 5 hours in a completely dissolved state at ℃, the reaction was completed.

The resulting reaction solution was cooled to 70° C., and at 70° C. or lower, 460 g of excess epichlorohydrin was recovered by vacuum distillation. Add isopropyl alcohol to this concentrate
og was added and stirred for 15 minutes at 60° C. or below, which separated into an oil layer and an alcohol layer. When this oil layer was discharged into 225 g of isopropyl alcohol which was being vigorously stirred, 55.7 g of a yellow powdery imide ring-containing epoxy resin was obtained.

The epoxy weight of this epoxy resin is 475.5g/eq
The softening point was 80 to 90°C.

The results of IR analysis are shown in Figure 4.

Examples 1 to 5, Comparative Example 1 The epoxy resin of the present invention shown in Table 1 was 3.3'-DAD
Using PS (3,3-diaminodiphenylsulfone) as a curing agent, casting was performed according to the curing schedule shown in Table 1, and the thermal properties and mechanical properties were measured.

Note that the results using bisphenol A type epoxy resin (trade name: Ebicoat 828 manufactured by Shell Chemical) were used as a comparative example.

The results are shown in Table 1.

Examples 6 to If The epoxidized products of various imide ring-containing diphenols obtained in Synthesis Examples 1 to 4 were used in combination with other known and commonly used epoxy resins, and various curing agents and curing accelerators were added as necessary. A blend was obtained which was melt-kneaded at 120 to 130°C.

(A) This formulation was heated at 150°C for 2 hours and then heated for 2 hours.
The resin was cured by heating at 00° C. for 2.5 hours.

Various properties were measured for each of the obtained cured products.

(B) Cold-rolled steel plate washed with trichlorethylene from each compound (JIS G 3141,5PCC/S0,25
X 100

The tensile shear adhesive strength of this material was measured at 20°C and 150°C.
Measured at. The results are shown in Table 2.

The following hardening agents were used.

a) Phenol novolac resin (trade name: BRG #5853, manufactured by Showa Kobunshi) b) Acid anhydride (trade name: Ebicure YH-306, manufactured by Yuka Shell Chemical) c) 4,4°-methylene dianiline comparative example 2.3 Epoxy resin obtained from bisphenol A (product name:
Ebicoat 828 Yuka Shell Chemical Co., Ltd., epoxy
fi 189g/eq), epoxy resin derived from phenolic novolac resin (trade name: DEN-4
31, Made by DOW Chemical, epoxy film
179 g/eq), and various properties were measured in the same manner as in the examples. The results are shown in Table 2.

〔Effect of the invention〕

The cured product obtained from the resin composition of the present invention shows a dramatic improvement in heat resistance due to the use of an epoxy resin containing an imide ring that does not participate in the curing reaction. Also, 2
．． It has a 2-bis(hydroxyphenyl)propane type skeleton and is cured by the epoxy group connected to it, so
It also shows excellent performance in terms of mechanical strength and adhesiveness.

[Brief explanation of the drawing]

Figure 1 is an IR spectrum diagram of the epoxy resin obtained in Synthesis Example 1, Figure 2 is an IR spectrum diagram of the epoxy resin obtained in Synthesis Example 4, and Figure 3 is an IR spectrum diagram of the epoxy resin obtained in Synthesis Example 5. IR spectrum diagram of epoxy resin FIG. 4 shows an IR spectrum diagram of the epoxy resin obtained in Synthesis Example 6. Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group) group group, fused polycyclic aromatic group, aromatic group directly,
or a non-fused polycyclic aromatic group interconnected by a bridge member, and the two hydroxy groups are both bonded to the meta or para position). Epoxy resin in which % or more is epoxidized. 2. A method for producing an imide ring-containing epoxy resin, which comprises reacting an imide ring-containing diphenol represented by the general formula (I) with epihalohydrin to epoxidize 50% or more of the hydroxyl groups of the imide ring-containing diphenol. 3. Imide ring-containing diphenols represented by general formula (I) and epihalohydrin are reacted in the presence of a hydrogen halide acceptor to epoxidize 50% or more of the hydroxyl groups of the imide-11-containing diphenols. Method for producing containing epoxy resin. 4. An epoxy resin composition comprising an epoxy resin component and a curing agent, the epoxy resin comprising 15% by weight or more of the epoxy resin according to claim 1 as the epoxy resin component in the total composition. Composition.